Polycarboxylic acid esters of polyunsaturated higher alcohols



Patented Dec. 7, 1937 UNITED. STATES v 8,101,221 nrcsnnoxx'uc scmcams onerou- Y mom swonors James H.

Wilmirigton. ELdnPoutdeNemonrs .minstomma Delusions-to & Company, Wlb' .of Delaware- No Application August- 13, 1035,

1: came. (oi. zoo-10s I This invention relates to new compositions of matter, and more particularly to polycarboxylic acid estersof long chain alcohols having two or more ethylenic double bonds. A- particularly Dr 5 ferred class coming'within the broad class isthat of the polycarbonlic acid esters of monohydric alcohols obtainable from drying oils by reduc tion of the ester group thereofto a carbinolgroup. Thih invention has an object-the preparation 10 of polycarboxylic acid esters of long chain polyunsaturated monohydric. alcohols. A further object is the provision'of a process for the manufacture of this class of esters. A further object is the preparation of cellulom derivative composi- 1B- appear hereinafter.

These objects are ing invention wherein a polycarboxylic acid, its anhydride, halide. or ester with a relatively volatile alcohol is reacted with a long chain polyunsaturated monohydric alcohol or monohydric aliphatic'alc'ohol mixture comprising the same, or wherein the sodium 'salt of the acid is reacted with a chloride or other inorganic acid ester of u the unsaturated alcohol or monohydric aliphatic alcohol mixture comprising the same.

Alcohols particularly, suited to the practice of this invention are those obtained from drying oils, especially China-wood oil, by reduction of the ester .group thereof to a.carbin'ol group. This latter reduction may be accomplished in one way -bymeansof sodiuminthepresenceofanalcohol.

A particularly eflicacious process whereby the sodium reduction is effected is disclosed in- Scott and Hensley application Serial No. 729,900, filed June 9, 1934 which has issued as-U. 3. Patent No. 2,019,022; In this process the divi e oil is dissolved in a sufilcient amount (2% to 10 times theweightoitheoil) ofasuitableinertaolvent 49 such as xylene.-tolue ne. or petroleum fractions high in parailin hydrocarbons and boiling up to 100' or even 180? 0. A suitablealcohol such as methyl. ethy n-b t l. o preie rimwowl. tert-butyl, or sec-butyl alcohol is added in amounteqmlto zm olsalcoholperester equivathen added slowly, withrapid agitatiomto a suspension of finely divided alkali metal. such as melting point of the alkali metal. em. 1oo'-no' 'Ciwhensodimnisnsed; Withhighlynmatussratedgl'yceridesofthechinawoomdl typeations employins these esters. Other objects accomplished by the follow-' lentoftheoiLLe.,8'molsalcoholpermol.of' glyceride. This alcohobglyceride solution is,

'andexerts thehanh ratio of ester group-to sodium, to alcohol of 1:6:4 is used, corresponding to 1 mol. glyceride, 18 atoms of sodium, and 12 mols of alcohol. alcohol mixture obtained in this way from Chinawood oil is a water-white viscous oil having an iodine number of 166, a refractive index of 1.4734, and a specific gravity of 0.8590. This Product is referred to hereinafter as China-wood oil alcohol. This alcohol has also been termed isodihydroeleo stearyl alcohol by Kawai J. Chem.

Soc. Japan 49 1227-3441928) Chem. Abstracts 24 63 (1930). In view of the iodine number 166 which corresponds to that of an octadecadienol it is probable that, in the sodium reduction of China-wood oil, a partial saturation of the double bonds takes place. The China-wood oil alcohol however still contains two or more ethylenic double bonds, which feature characterizes all the alcohols employed herein.-

Having outlined above the generaf principlesz and purposes of the invention it may be stated in amplification that simple or mixed esters of The.

the polyunsaturated long chain alcohols with polycarboxylic acidsmay be made in various ways of which the foliowingexamples are illustrative but not limitative:

Emple 1.The diphthalate of China-wood oil alcohol one himdred six parts by weight of China-wood oil alcohol, 38.8 parts by weight of dimethyl phthalate, 5.5 parts by weight of litharge and 150 parts by weight of toluene were heated under a 'suitablefractionating column until the distilling temperature was constant at 108 C. The solution was filtered and the filtrate steam distilled. Theaqueous nwas saturated with salt,

extracted-with ether and the ether. solution dried .w'un sodium sulfate. After filtering and evaporailing the ether a light orange colored liquid was obtained. The ester had, a saponification num ber oi 171.5, the theoretical value for the diester being 170. s mple lie-Acid phenomena of chm-wood on Two hundred sixty-five parts. by weight of half hours at 140' 0. D e acid number was 143,

thecalculatedvalueforthe.halfesterbeing185.'

I chinaewood oil alcohol was-heated with 148 parts by weisht of phthalic anhydride for one and one-' 50 1 a reflux condenser for three hours.

Example 3."-Maleate of China-wood oil alcohol Two hundred sixty-five parts by weight ,of China-wood oil alcohol, 147 parts by weight of maleic anhydride, and 50 parts by weight of benzene were heated on the steam bath under The benzene solution was washed with water and the benzene evaporated. When chilled in ice water, the clear oil became crystalline. The acid number of the product was 155.

Example 4.--Tri-ester of citric (101; with China wood 'oil alcohol Seventy-nine and five-tenths parts by weight of China-wood oil alcohol, 27.6 parts by weight of triethyl citrate, 100 cc'of toluene and 3 parts by weight of litharge were heated under a 4- foot fractionating column until the distilling tem-' perature was constant at 108 C. This required 2 hours. The product was filtered, washed with water and the toluene removed by heating under vacuum. The light yell'ow'liquid product had a saponification number of 166, the calculated value for the tri-ester being 180.

Ten parts by weight of this ester and 2 parts by weight of a 1% benzene solution of cobalt linoleate were mixed together and spread out in a thin film. After 24 hours exposure to the air the film had hardened to a tough coating. This is a property not shared by corresponding esters of alcohols having a lower degree of unsaturaf tion.

Example "5.Neutral phtltalate of a mixture of stearyl alcohol and China-wood oil alcohol Fifty-three parts by weight of China wood oil alcohol, 54' parts by weight of octadecanol-l, 38.8 parts by weight of dimethyl phthalate, 4.5 parts by weight of litharge and 150 parts by weight of toluene were heated under a suitable fractionating column until the distilling temperature was constant at 108 C. The solution was illtered and the filtrate steam distilled. The aqueous suspension was saturated withsalt, extracted with ether and the ether solution dried with sodium sulfate. iA-fter.,- filtering and evaporating the ether a light colored low melting solid was obtained. The product was probably a mixture chain length to" the acids which are major constituents of drying and semi-drying oils (the alcohol differing from the acid in having a carbinol group in place of the carboxyl group) are' a particularly preferred class of alcohols and are obtainable by the carboxyl reduction of polyunsaturated fatty acid radicals occuring to a substantial amount, that is, at least 10%, in drying and semi-drying oils. They include therefore the polyunsaturated alcohols obtained by the carboxylic reduction of drying oils or drying oil acids such .as linseed oil, China-wood oil, perilla oil, soya bean oil, and the fatty acids derived valuable in the manufacture of coatin nd plastic compositions containing cellulose derivatives,

from their saponification, such as linolic acid,

eleostearic acid, linolenic acid, etc. Further, the

polyunsaturated alcohols obtainable by sodium reduction of marine animal oils which are rich in the glycerides of highly unsaturated acids, examplesof such oils being herring oil, sardine oil, and shark oil.

While-certain acids have been given in illustration, the process is generally applicable to polycarboxylic acids, further examples of which are, adipic, fumaric, maleic, succinic, malic, itaconic, glutaric, tricarballylic, azelaic, pimelic, trimesic, sebacic, suberie, .quinolinic, diphenic, naphthalic, citric, hexahydrophthalic, 'tetrahydrophthalimmalonic, mucic, citraeonie, trimellitic, tartaric, etc. acids. Ester compositions comprising these p'o'lycarboxylic acid-esters may also include, monocarboxylic acids and there may therefore also be employed abietic acid, propionic acid, benzoic acid, salicylic acid, naphthenic acids, lactic acid, oleic acid, linoleic acid, elecstearic acid, chloroacetic acid, ricinoleic acid,

etc.

The methods for the preparation of the esters described above are capable of considerable variation. .The constituents of the reaction mixture may be varied. Catalysts other than-those mentioned may be used, or solvents may be u;ed without the use of any catalyst. 1

The polycarboxylic acid esters of unsaturated alcohols mentioned herein inc iide esters in which at least one ofthe alcohol groups is polyunsaturated, part or all of the remaining acid radicals of the acids being either unesterified or esterifled with saturated or unsaturated alcohols. Mixed esters containing in addition to the polyunsaturated alcoholradicals, other alcohol radicals such as those of methyl, ethyl, butyL-octyl,

dcde'cyl, hexadecyl, 9, 10-oetadecenyl, octadecyl cyclohexyl, benzyl, ethoxyethyl, etc. alcohols may also be prepared according to the disclosure of this specification, for example by reacting a mixture of alcohols comprising a. polyunsaturated alcohol and an alcohol having less than two double bonds with the acid or acid anhydride in the presence of a catalyst'such as hydrochloric or, preferably, sulfuric acid, or by reaction or the mixture of the two types of alcohols with a polycarboxylic acid ester ofan alcohol -more volatile than either.

The esters prepared as above described vary from waterwhite to pale amber liquids or low melting solids. They are insoluble in water but are readily soluble in alcohol, acetone,ethyl acetate, butyl acetate, benzene, xylene, ether, etc. They are compatible when mixed in equal proportions with nitrocellulose and are compatible in lower ratios with cellulose 'ethers and other cellulose esters. These new esters are e particularly those from mixtures of aturated and uable for the preparation of all types of composi-- tions containing cellulose esters and ethers. In particular they maybe used in the preparation aionaav tor coating fabrics, paper, etc.,- and in plastic compositions to be used in the preparation of toiletware, novelties, sheeting, rods, tubes, safety the polyunsaturated hydrocarbon alcohol obtainable by the carboxyl replaced by radical of an reduction of the acid radicals of a drying oil.

Patent.No. 2,1o1,227.

JAMES H. wERNTz.

d3 5. An ester 'of a polycarboxylic acid wherein the hydrogen atom of at least one carboxyl group .is replaced by the polyunsaturated hydrocarbon radical of an alcohol obtainable by the carboxyl boxyl reduction of China-wood oil.

CERTIFICATE OF CORRECTION.

5 glass, etc. They may also be used in cellulose reduction of the acid radicals of a drying oil, and l derivative adhesive compositions. the hydrogen atom of another carboxyl group is The esters of this invention show a pronounced replaced by the radical of a diflerent alcohol. tendency toward auto-oxidation, particularly in 6. An acid ester of a polycarboxyiic acid wherethe presence of catalysts such as cobaltlinoleate, in the hydrogen atom of at least one carboxyl to form hard films.- This behavior is especially group isreplaced by the polyunsaturated hydrol0 noticeable when the esters are made with carcarbon radical of an alcohol obtainable by the bonlic acids of three or more acid groups such carboxyl reduction of the acid radicals oi Chinaasthe citrate esters. The use of the suliated wood .oil.

or suli'onated esters as wetting agents and deter- '7. A polycarboxylic acid ester of a polyun- 18 gents is disclosed in Werntz application Serial saturated monohydric alcohol 0! at least car- 15 No. 757,465, filed December 14, 1934, of which the hon atoms. present application is a continuation in part. 8. Process for the preparation 01' a polyca v The above description and specific examples boxylic acid ester of apolyunsaturated long chain are given for illustration only. Any modification alcohol, which comprises reacting said alcohol 20- of or variation therefrom which conforms to the with a member of the class consisting of polyspirit of the invention is intended to be included carboxylic acids, their anhydrides, their acid within the scope or the claims. halides, and their esters with more volatile al- I claim: cohols. 1. An ester of a polycarboxylic acid wherein -9. A citric acid ester of a polyunsaturated long the hydrogen atom of at least one carboxyl group chain alcohol obtainable by the sodium reduction 25 is replaced by the polyunsaturated hydrocarbon of China-wood oil. radical of an alcohol obtainable by the carboxyl 10. A phthalic acid ester oi a'polyunsaturated reduction of the acid radicals of Chinawood oil. long chain alcohol obtainable by the sodium re- 2. An ester of a polycarboxylic acid wherein duction of China-wood oil.

the hydrogen atoms of the carboxyl groups are 11. A neutral phthalic acid ester of a polyunreplaced by the polyunsaturated hydrocarbon saturated long chain alcohol obtainable by the radical of an alcohol obtainable by the carboxyl sodium reduction of China-wood oil.

reduction of the acid radicals of China-wood oil. 12. An ester composition obtained by esterify- 3. An ester of apolycarboxylic acid wherein the ing a polycarboxylic acid with a mixture of alihydrogen atom of at least one carboxyl group is phatic monohydric alcohols containing in pre- 85 replaced by the polyunsaturated hydrocarbon dominant amount a polyunsaturated monohydric radical of an alcohol obtainable by the carboxyl alcohol of at least 15 carbon atoms. reduction-of the acid radicals of a drying oil. 13. An ester composition obtainable by esteri- 4. An ester of a polycarboxylic acid "wherein tying a polycarboxylic acid with the mixture of Q the hydrogen atoms of the carboxyl groups are polyunsaturated alcohols obtainable by the car- 40 December T, 1957.

It ishereby certified that error appears in the printed" specification of the above numbered'patent r-equiring correctionas follows Page 2, first column, line 51,- for the word "octadecanal read oetadecanol; and that the said Letters Patent should be read with this correction therein thatthe same may conf orm to the record of the case in the Patent Office.

Signed and sealed this 15th day or February; A. D. 1958.

Henry Van Arsdale,

Acting Commissioner of Patents" (Seal) tor coating fabrics, paper, etc.,- and in plastic compositions to be used in the preparation of toiletware, novelties, sheeting, rods, tubes, safety the polyunsaturated hydrocarbon alcohol obtainable by the carboxyl replaced by radical of an reduction of the acid radicals of a drying oil.

Patent .No. 2,1o1,227.

JAM S H. wERNlZ.

d3 5. An ester 'of a polycarboxylic acid wherein the hydrogen atom of at least one carboxyl group .is replaced by the polyunsaturated hydrocarbon radical of an alcohol obtainable by the carboxyl boxyl reduction of China-wood oil.

CERTIFICATE OF CORRECTION.

5 glass, etc. They may also be used in cellulose reduction of the acid radicals of a drying oil, and l derivative adhesive compositions. the hydrogen atom of another carboxyl group is The esters of this invention show a pronounced replaced by the radical of a diflerent alcohol. tendency toward auto-oxidation, particularly in 6. An acid ester of a polycarboxyiic acid wherethe presence of catalysts such as cobaltlinoleate, in the hydrogen atom of at least one carboxyl to form hard films.- This behavior is especially group isreplaced by the polyunsaturated hydrol0 noticeable when the esters are made with carcarbon radical of an alcohol obtainable by the bonlic acids of three or more acid groups such carboxyl reduction of the acid radicals oi Chinaasthe citrate esters. The use of the suliated wood .oil.

or suli'onated esters as wetting agents and deter- '7. A polycarboxylic acid ester of a polyun- 18 gents is disclosed in Werntz application Serial saturated monohydric alcohol 0! at least car- 15 No. 757,465, filed December 14, 1934, of which the hon atoms. present application is a continuation in part. 8. Process for the preparation 01' a polyca v The above description and specific examples boxylic acid ester of apolyunsaturated long chain are given for illustration only. Any modification alcohol, which comprises reacting said alcohol 20- of or variation therefrom which conforms to the with a member of the class consisting of polyspirit of the invention is intended to be included carboxylic acids, their anhydrides, their acid within the scope or the claims. halides, and their esters with more volatile al- I claim: cohols. 1. An ester of a polycarboxylic acid wherein -9. A citric acid ester of a polyunsaturated long the hydrogen atom of at least one carboxyl group chain alcohol obtainable by the sodium reduction 25 is replaced by the polyunsaturated hydrocarbon of China-wood oil. radical of an alcohol obtainable by the carboxyl 10. A phthalic acid ester oi a'polyunsaturated reduction of the acid radicals of Chinawood oil. long chain alcohol obtainable by the sodium re- 2. An ester of a polycarboxylic acid wherein duction of China-wood oil.

the hydrogen atoms of the carboxyl groups are 11. A neutral phthalic acid ester of a polyunreplaced by the polyunsaturated hydrocarbon saturated long chain alcohol obtainable by the radical of an alcohol obtainable by the carboxyl sodium reduction of China-wood oil.

reduction of the acid radicals of China-wood oil. 12. An ester composition obtained by esterify- 3. An ester of apolycarboxylic acid wherein the ing a polycarboxylic acid with a mixture of alihydrogen atom of at least one carboxyl group is phatic monohydric alcohols containing in pre- 85 replaced by the polyunsaturated hydrocarbon dominant amount a polyunsaturated monohydric radical of an alcohol obtainable by the carboxyl alcohol of at least 15 carbon atoms. reduction-of the acid radicals of a drying oil. 13. An ester composition obtainable by esteri- 4. An ester of a polycarboxylic acid "wherein tying a polycarboxylic acid with the mixture of Q the hydrogen atoms of the carboxyl groups are polyunsaturated alcohols obtainable by the car- 40 December T, 1957.

It ishereby certified that error appears in the printed" specification of the above numbered'patent r-equiring correctionas follows Page 2, first column, line 51,- for the word "octadecanal read oetadecanol; and that the said Letters Patent should be read with this correction therein thatthe same may conf orm to the record of the case in the Patent Office.

si ned and sealed this 15th day or February, A. D. 1958.

Henry Van Arsdale,

Acting Commissioner of Patents" seal) 

